CN101049953A - Microballons of laminar dual hydroxy composite metal oxide and preparation method - Google Patents
Microballons of laminar dual hydroxy composite metal oxide and preparation method Download PDFInfo
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- CN101049953A CN101049953A CNA2007100626496A CN200710062649A CN101049953A CN 101049953 A CN101049953 A CN 101049953A CN A2007100626496 A CNA2007100626496 A CN A2007100626496A CN 200710062649 A CN200710062649 A CN 200710062649A CN 101049953 A CN101049953 A CN 101049953A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/007—Mixed salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
- C01F7/784—Layered double hydroxide, e.g. comprising nitrate, sulfate or carbonate ions as intercalating anions
- C01F7/785—Hydrotalcite
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Abstract
This invention relates to a method for preparing lamellar dihydroxyl composite metal oxide microspheres. The method comprises: preparing lamellar dihydroxyl composite metal oxide (hydrotalcite) nano- or submicro-particles by co-precipitation, nucleation/crystallization/isolation, nonequilibrium crystallization or hydrothermal synthesis, preparing into slurry with a certain solid content, adding bonding agent, spin-spraying for granulation, and drying to obtain microspheres with diameters of 5-100 mu.m. The bulk density, specific surface area, pore volume and most probable pore diameters of the microspheres are 0.4-0.8 g/cm3, 40-150 m2/g, 0.1-0.8 cm3/g and 2-40 nm, respectively. The microspheres can be directly used for catalysis or separation after activated, and the mass transfer resistance and carbon accumulation are minimized.
Description
Technical field
The present invention relates to a kind of layered di-hydroxyl composite metal oxidate microspheres and preparation method thereof, being specifically related to a kind of is the molding, granulating method of construction unit to have strong inflexible nanometer or submicron order layered di-hydroxyl composite metal oxidate particulate.
Background technology
Hydrotalcite-based compound comprises hydrotalcite (Hydrotalcite) and houghite (Hydrotalcite-likecompound), its main body generally is made of the oxyhydroxide of two kinds of metals, therefore be called layered di-hydroxyl composite metal oxidate (Layered Double Hydroxide is abbreviated as LDH) again.The intercalation compound of LDH is called intercalated houghite.Hydrotalcite, houghite and intercalated houghite are referred to as hydrotalcite intercalation material (LDHs).This material is six side's laminated structures, and lamella itself has extremely strong rigidity, the extremely difficult controlled sheet structure of pattern of preparing.Such material is a kind of inorganic materials with unique structural characteristics: having established this class material as elementary composition adjustable sex change, the adjustable sex change of pore structure and designability of interlayer intercalant anion kind etc. in relative broad range might become the commercial catalysts with potential application foreground or the basis of catalyst precursor.Especially, this class material is through high-temperature roasting, the laminate metallic cation can change homodisperse complex metal oxides with spinel structure on molecular scale into, therefore, we can be by obtaining to have the catalyzer or the support of the catalyst of specific catalytic performance to designs such as the kind of laminate metallic cation and proportionings.
As everyone knows, when catalytic applications, catalyzer usually needs could use after the moulding, moulding helps increasing the physical strength of catalyzer on the one hand, helps the Separation and Recovery of catalyzer and utilization once more on the other hand, yet, all use houghite materials are for as catalyst precursor the time in the document, all use powder body material, therefore, have extremely strong inflexible houghite forming materials and will help improving the catalytic effect of catalyzer and separating and recovery of different-phase catalyst this.
When shaping of catalyst, often need to add the purpose that a certain proportion of tackiness agent reaches assistant formation.Tackiness agent is a class by means of surface bond and internal force (adhesive power and force of cohesion etc.) effect, can make the general name of the non-metallic material that a solid surface and another solid surface combine.This class material is can play the raw material of cohesive action, be aided with solvent, softening agent, tackifier, linking agent, solidifying agent, permeate agent and filler etc., by physics, chemistry or both combine composition that the method used is mixed with complicated can be at the interfacial phase agglutinating mixed system of two articles.
At document J.Am.Chem.Soc.2002,124 (47): among the 14127-14136, people such as Choudary B.M. have studied when with the layered di-hydroxyl composite metal oxidate being the reactions such as Heck-, Suzuki-, Sonogashira-and Stille-of the pillared metal Pd catalysis of carrier (or basic ligands) chlorinated aromatic hydrocarbons compound, show the excellent properties of catalysis C-C coupled reaction.
At document Angew.Chem.Int.Edit.2001,40 (4): among the 763-766, people such as Choudary B.M. have studied the product of NiAlLDHs after rehydrated activation first and can catalysis be transformed into carbonyl compound as the alcohol compound that contains allyl group, benzyl or α keto-alcohol under relatively mild condition in the presence of the molecular oxygen, and point out this process not only economically feasible but also the extensive reaction that suits to be applied to.
At document React.Kinet.Catal.Lett.2000,69 (2): among the 223-229, Das, J. and Parida, K. have studied the houghite material of different Zn/Al behind 450 ℃ of calcination activations, demonstrate the activity of good catalysis cupric acetate glycosylation reaction.
In above-mentioned document, the houghite material has shown good catalytic effect as catalyst precursor, and still, such material all adds with the powder form in use, and this has brought adverse influence for catalyst separating and recycling after reaction finishes.Therefore, the houghite material is carried out the moulding preparation and will help catalyst separating and recycling.
Summary of the invention
The purpose of this invention is to provide a kind of layered di-hydroxyl composite metal oxidate microspheres and preparation method thereof, be construction unit promptly to have strong inflexible nanometer or submicron order layered di-hydroxyl composite metal oxidate particulate, with the tackiness agent is auxiliary material, utilize common industrial spray drying device, realize the direct preparation of the layered di-hydroxyl composite metal oxidate material of microballoon form first.Promptly at first utilize methods such as common houghite preparation methods such as coprecipitation method, nucleation crystallization/isolation method, non-equilibrium crystallization method or hydro-thermal be synthetic to prepare layered di-hydroxyl composite metal oxidate (houghite) particle of particle diameter for nano level or submicron order, the amount of tackiness agent that adds by modulation and water is mixed with the colloidal state slurries of different binder contents and solid content then, and last is initial material is realized the material of microballoon form on industrial spray drying device preparation with the colloidal state slurries.Can be directly used in catalysis or separation field after this material is activated, not need, and excellent pore passage structure can reduce resistance to mass transfer and reduce the generation of carbon distribution through formative stage once more.
Layered di-hydroxyl composite metal oxidate microspheres provided by the invention, its chemical general formula is:
[M
II 1-xM
III x(OH)
2]
x+·(A
n-)
x/n·mH
2O
Wherein, M
IIBe Mg
2+, Ni
2+, Zn
2+, Cu
2+, Co
2+, Ca
2+Or Fe
2+In one or both; M
IIIBe Al
3+, Cr
3+, Ga
3+, In
3+, Co
3+, Fe
3+Or V
3+In any one or two kinds;
The particle diameter of this microballoon between 5～100 μ m, median size d
(0.5)=20～25 μ m, bulk density are 0.4～0.8g/cm
3, specific surface area is at 20～150m
2Between/the g; Pore volume is in 0.1～0.8cm
3Between/the g, the most probable pore size distribution is between 2～40nm; This microballoon is a solid sphere.
Concrete preparation process of the present invention is as follows:
At first prepare nano level or submicron order houghite, the preparation method of houghite is a known technology, that adopts at present has methods such as coprecipitation method, nucleation/crystallization isolation method, non-equilibrium crystallization method or hydro-thermal be synthetic, wherein preferred methods is nucleation/crystallization isolation method, both having adopted the mixed liquid film reactor that is all-trans to carry out nucleation and having seen (ZL00132145.5), carry out crystallization (seeing ZL00132146.3) by temperature programmed control dynamic crystallization method again, this method can obtain nano level or submicron order houghite, and narrow distribution.
The invention is characterized in:
A: will prepare but the houghite colloidal substances do deionized water thorough washing handled without super-dry, the pH that makes supernatant liquor is 7～8, adds that to be made into solid content after deionized water fully stirs be 1～20% slurries again;
Used houghite materials chemistry general formula is: [M
II 1-xM
III x(OH)
2]
X+(A
N-)
X/nMH
2O
Wherein, M
IIBeing divalent metal, can be Mg
2+, Ni
2+, Zn
2+, Cu
2+, Co
2+, Ca
2+Or Fe
2+Deng in one or both; M
IIIBeing trivalent metal cation, can be Al
3+, Cr
3+, Ga
3+, In
3+, Co
3+, Fe
3+Or V
3+Wait any one or two kinds;
B: add the tackiness agent that accounts for slurries gross weight 0.5～10% in the houghite slurries of steps A, fully stirring makes system be even colloidal state shape;
Used tackiness agent both can be natural glue such as starch, protein, dextrin, gelatin etc., also can be the tackiness agent of synthetic such as synthetic resins, polyvinyl alcohol, water glass etc.;
C: the colloidal state slurries of step B are squeezed into the flow velocity of 1～30mL/min on the atomizing wheel disc of rotary spray-dryer with constant flow pump, regulated the atomizing wheel rotating speed at 1.0～2.0 ten thousand rev/mins, spraying drying ingress temperature is between 110 ℃～180 ℃.Wherein preferable operational condition is: the atomizing wheel rotating speed is 1.2～1.5 ten thousand rev/mins, and input speed is 5～20mL/min, and inlet temperature is between 140 ℃～160 ℃.
Adopt Shimadu XRD-6000 type powder x-ray diffraction that the coccoid of preparation is carried out qualitative analysis, the result is as follows:
Fig. 1 is the XRD spectra of the material that obtained, wherein 1a, 1b and 1c are respectively the spectrogram of embodiment 1,2,3 and 4 samples, (003) of houghite material, (006), (012), (015), (110) and (113) characteristic peak have all occurred as seen from the figure, illustrate that prepared material is layered di-hydroxyl composite metal oxidate (houghite).
Adopt Hitachi-S3500N type SEM to carry out the sample topography analysis, the result is as follows:
Fig. 2 is that what to contain that the colloidal state slurries of 1%PVA and 2% solid content are obtained is the microballoon SEM picture of construction unit with MgAlLDHs for embodiment 1, and wherein 2a--c is the picture of amplification step by step of sample, and as seen from the figure, prepared microballoon sphericity is good; Fig. 2 d adopts the microballoon sectional view of back scattering scanning electron imaging technique (BSEM) acquisition for after microballoon is carried out resin embedding after the cutting polishing, the result shows that prepared microballoon is a solid sphere.
What Fig. 3 contained that the colloidal state slurries of 5% Zulkovsky starch and 2.5% solid content are obtained for embodiment 4 is the microballoon SEM picture of construction unit with ZnAlLDHs, and wherein 3a-c is respectively the picture of amplification step by step of sample, and as seen from the figure, prepared microballoon sphericity is good; Fig. 3 d adopts the microballoon sectional view of back scattering scanning electron imaging technique (BSEM) acquisition for after microballoon is carried out resin embedding after the cutting polishing, the result shows that prepared microballoon is a solid sphere.
What Fig. 4 contained that the colloidal state slurries of 1%PVA and 3% solid content are obtained for embodiment 6 is the microballoon SEM picture of construction unit with NiAlLDHs, and wherein 4a-c is the picture of amplification step by step of sample, and as seen from the figure, prepared microballoon sphericity is good; Fig. 4 d adopts the microballoon sectional view of back scattering scanning electron imaging technique (BSEM) acquisition for after microballoon is carried out resin embedding after the cutting polishing, the result shows that prepared microballoon is a solid sphere.
What Fig. 5 contained that the colloidal state slurries of 1%PVA and 4% solid content are obtained for embodiment 9 is the microballoon SEM picture of construction unit with CuZnAlLDHs (Cu: Zn: Al=1: 2: 1.5), wherein 5a-b is the picture of amplification step by step of sample, as seen from the figure, prepared microballoon sphericity is good.
What Fig. 6 contained that the colloidal state slurries of 5% Zulkovsky starch and 5% solid content are obtained for embodiment 10 is the microballoon SEM picture of construction unit with CuZnAlLDHs (Cu: Zn: Al=1: 2: 1), wherein 6a-b is the picture of amplification step by step of embodiment 1 sample, as seen from the figure, prepared microballoon sphericity is good.
Distinguishing feature of the present invention is the effect by means of tackiness agent, and preparing to have strong inflexible layered di-hydroxyl composite metal oxidate particulate first is the microballoon of construction unit.Adopt method provided by the invention to prepare layered di-hydroxyl composite metal oxidate microspheres, its preparation method is easy, suitability for industrialized production.
Description of drawings
Fig. 1 is the XRD spectra of embodiment 1,2,3,4 and 5 prepared microballoons, and wherein 1d is the feature spectrogram of embodiment 4 and 5;
Fig. 2 is the SEM picture of amplification step by step and the section BSEM figure of the microballoon that obtained of embodiment 1;
Fig. 3 is the SEM picture of amplification step by step and the section BSEM figure of the microballoon that obtained of embodiment 4;
Fig. 4 is the SEM picture of amplification step by step and the section BSEM figure of the microballoon that obtained of embodiment 6;
Fig. 5 is the SEM of the amplification step by step picture of embodiment 9 prepared microballoons;
Fig. 6 is the SEM of the amplification step by step picture of embodiment 10 prepared microballoons.
Fig. 7 is the SEM of the amplification step by step picture of embodiment 11 prepared microballoons;
Fig. 8 is the SEM of the amplification step by step picture of embodiment 13 prepared microballoons.
Embodiment
The invention will be further described below in conjunction with embodiment:
A: take by weighing 61.54g Mg (NO
3)
26H
2O and 45.02g Al (NO
3)
39H
2O is dissolved in and is made into the 300mL mixing salt solution in the deionized water; And then take by weighing 23.04g NaOH and 25.44g Na
2CO
3Be dissolved in and be made into the 300mL mixed ammonium/alkali solutions in the deionized water; Above-mentioned two kinds of mixing solutionss are added full back-mixing liquid film reactor simultaneously, slit width between conditioned reaction device rotor and the stator is 0.02mm, operating voltage is 100V, rotor speed is 4000rpm, to stir in the mixed serum adding crystallizing kettle that obtain, keeping the temperature of mixed serum in the still is 95-105 ℃ of backflow crystallization 6 hours, obtains the magnesia-alumina hydrotalcite;
B: the product deionized water thorough washing of steps A preparation, the pH that makes supernatant liquor is 7～8, adds that to be made into solid content after deionized water fully stirs be 2% slurries again;
C: add the PVA that accounts for slurries gross weight 1% in the houghite slurries of step B, fully stirring makes system be even colloidal state shape;
D: the colloidal state slurries of step C are squeezed on the atomizing wheel disc with 1.2 ten thousand rev/mins of high speed rotating with the flow velocity of 6～10mL/min with constant flow pump, and to set spraying drying ingress temperature be 150 ℃, carry out mist projection granulating; The specific surface area of the spheroidal particle that is obtained is 39.76m
2/ g, total pore volume is 0.31mL/g, the most probable aperture is 32.5nm.
Embodiment 2
A: with embodiment 1;
B: with embodiment 1;
C: add the PVA that accounts for slurries gross weight 5% in the houghite slurries of step B, fully stirring makes system be even colloidal state shape;
D: the colloidal state slurries of step C are squeezed on the atomizing wheel disc with 1.2 ten thousand rev/mins of high speed rotating with the flow velocity of 6～10mL/min with constant flow pump, and to set spraying drying ingress temperature be 150 ℃, carry out mist projection granulating.
Embodiment 3
A: with embodiment 1;
B: with embodiment 1;
C: add the PVA that accounts for slurries gross weight 10% in the houghite slurries of step B, fully stirring makes system be even colloidal state shape;
D: the colloidal state slurries of step C are squeezed on the atomizing wheel disc with 1.2 ten thousand rev/mins of high speed rotating with the flow velocity of 6～10mL/min with constant flow pump, and to set spraying drying ingress temperature be 150 ℃, carry out mist projection granulating.
Embodiment 4
A: take by weighing 71.39g Zn (NO
3)
26H
2O and 45.02g Al (NO
3)
39H
2O is dissolved in and is made into the 300mL mixing salt solution in the deionized water; And then take by weighing 23.04g NaOH and 25.44g Na
2CO
3Be dissolved in and be made into the 300mL mixing salt solution in the deionized water; The nucleation crystallization condition is prepared zinc-aluminum gavite with embodiment 1;
B: the product deionized water thorough washing of steps A preparation, the pH that makes supernatant liquor is 7～8, adds that to be made into solid content after deionized water fully stirs be 2.5% slurries again;
C: add the Zulkovsky starch that accounts for slurries gross weight 5% in the houghite slurries of step B, fully stirring makes system be even colloidal state shape;
D: the colloidal state slurries of step C are squeezed on the atomizing wheel disc with 1.2 ten thousand rev/mins of high speed rotating with the flow velocity of 6～10mL/min with constant flow pump, and to set spraying drying ingress temperature be 150 ℃, carry out mist projection granulating; The specific surface area of the spheroidal particle that is obtained is 25.45m
2/ g, total pore volume is 0.16mL/g, the most probable aperture is 32.6nm.
Embodiment 5
A: with embodiment 4;
B: with embodiment 4;
C: add the Zulkovsky starch that accounts for slurries gross weight 10% in the houghite slurries of step B, fully stirring makes system be even colloidal state shape;
D: the colloidal state slurries of step C are squeezed on the atomizing wheel disc with 1.2 ten thousand rev/mins of high speed rotating with the flow velocity of 6～10mL/min with constant flow pump, and to set spraying drying ingress temperature be 150 ℃, carry out mist projection granulating.
Embodiment 6
A: take by weighing 69.79g Ni (NO
3)
26H
2O and 45.02g Al (NO
3)
39H
2O is dissolved in and is made into the 300mL mixing salt solution in the deionized water; And then take by weighing 28.80g NaOH and 25.44g Na
2CO
3Be dissolved in and be made into the 300mL mixing salt solution in the deionized water; Nucleation, crystallization condition are prepared nickel aluminium houghite with embodiment 1;
B: the product deionized water thorough washing of steps A preparation, the pH that makes supernatant liquor is 7～8, adds that to be made into solid content after deionized water fully stirs be 3% slurries again;
C: add the PVA that accounts for slurries gross weight 1% in the houghite slurries of step B, fully stirring makes system be even colloidal state shape;
D: the colloidal state slurries of step C are squeezed on the atomizing wheel disc with 1.2 ten thousand rev/mins of high speed rotating with the flow velocity of 6～10mL/min with constant flow pump, and to set spraying drying ingress temperature be 150 ℃, carry out mist projection granulating; The specific surface area of the spheroidal particle that is obtained is 111.37m
2/ g, total pore volume is 0.62mL/g, the most probable aperture is 18.13nm.
Embodiment 7
A: with embodiment 6;
B: with embodiment 6;
C: add the PVA that accounts for slurries gross weight 5% in the houghite slurries of step B, fully stirring makes system be even colloidal state shape;
D: the colloidal state slurries of step C are squeezed on the atomizing wheel disc with 1.2 ten thousand rev/mins of high speed rotating with the flow velocity of 6～10mL/min with constant flow pump, and to set spraying drying ingress temperature be 150 ℃, carry out mist projection granulating.
Embodiment 8
A: with embodiment 6;
B: with embodiment 6;
C: add the PVA that accounts for slurries gross weight 10% in the houghite slurries of step B, fully stirring makes system be even colloidal state shape;
D: the colloidal state slurries of step C are squeezed on the atomizing wheel disc with 1.2 ten thousand rev/mins of high speed rotating with the flow velocity of 6～10mL/min with constant flow pump, and to set spraying drying ingress temperature be 150 ℃, carry out mist projection granulating.
Embodiment 9
A: take by weighing 19.33g Cu (NO
3)
26H
2O, 47.6g Zn (NO
3)
26H
2O and 45.02g Al (NO
3)
39H
2O is dissolved in and is made into the 300mL mixing salt solution in the deionized water; Take by weighing 28.80g NaOH and 25.44g Na again
2CO
3Be dissolved in and be made into the 300mL mixed ammonium/alkali solutions in the deionized water; The nucleation condition is with embodiment 1, and crystallization then is to stir 12 hours under the condition of atmospheric pressure at room, preparation copper zinc-aluminium ternary houghite;
B: the product deionized water thorough washing of steps A preparation, the pH that makes supernatant liquor is 7～8, adds that to be made into solid content after deionized water fully stirs be 4% slurries again;
C: add the PVA that accounts for slurries gross weight 1% in the houghite slurries of step B, fully stirring makes system be even colloidal state shape;
D: the colloidal state slurries of step C are squeezed on the atomizing wheel disc with 1.2 ten thousand rev/mins of high speed rotating with the flow velocity of 6～10mL/min with constant flow pump, and to set spraying drying ingress temperature be 150 ℃, carry out spray drying granulation; The specific surface area of the spheroidal particle that is obtained is 90.6m
2/ g, total pore volume is 0.65mL/g, the most probable aperture is 32nm.
A. take by weighing 21.74g Cu (NO respectively
3)
26H
2O, 53.55g Zn (NO
3)
26H
2O and 33.76gAl (NO
3)
39H
2O is dissolved in and is made into the 300mL mixing salt solution in the deionized water; Take by weighing 28.80g NaOH and 19.08g Na again
2CO
3Be dissolved in and be made into the 300mL mixed ammonium/alkali solutions in the deionized water; Nucleation, crystallization condition prepare copper zinc-aluminium ternary houghite with embodiment 9;
B: the product deionized water thorough washing of steps A preparation, the pH that makes supernatant liquor is 7～8, adds that to be made into solid content after deionized water fully stirs be 5% slurries again;
C. add the Zulkovsky starch that accounts for slurries gross weight 5% in the houghite slurries of step B, fully stirring makes system be even colloidal state shape;
D: the colloidal state slurries of step C are squeezed on the atomizing wheel disc with 1.2 ten thousand rev/mins of high speed rotating with the flow velocity of 6～10mL/min with constant flow pump, and to set spraying drying ingress temperature be 150 ℃, carry out spray drying granulation; The specific surface area of the spheroidal particle that is obtained is 91.81m
2/ g, total pore volume is 0.70mL/g, the most probable aperture is 33.6nm.
Embodiment 11
A: take by weighing 30.77g Mg (NO
3)
26H
2O and 22.51g Al (NO
3)
39H
2O is dissolved in and is made into the 300mL mixing salt solution in the deionized water; Take by weighing 14.4g NaOH and 3.18g Na again
2CO
3Be dissolved in and be made into the 300mL mixed ammonium/alkali solutions in the deionized water; Low whipping speed is under 500 rev/mins the condition, dropwise to add mixing salt solution in the mixed ammonium/alkali solutions; Perhaps mixed ammonium/alkali solutions is dropwise added in the mixing salt solution, during the control rate of addition be 10mL/min, endpoint pH is controlled between 9.5～10, crystallization 12 hours under 65 ℃ of conditions is prepared the magnesia-alumina hydrotalcite material then;
B: the product deionized water thorough washing of steps A preparation, the pH that makes supernatant liquor is 7～8, adds that to be made into solid content after deionized water fully stirs be 2% slurries again;
C: add the PVA that accounts for slurries gross weight 1% in the houghite slurries of step B, fully stirring makes system be even colloidal state shape;
D: the colloidal state slurries of step C are squeezed on the atomizing wheel disc with 1.2 ten thousand rev/mins of high speed rotating with the flow velocity of 6～10mL/min with constant flow pump, and to set spraying drying ingress temperature be 150 ℃, carry out mist projection granulating.
Embodiment 12
A: take by weighing 30.77g Mg (NO
3)
26H
2O and 22.51g Al (NO
3)
39H
2O is dissolved in and is made into the 300mL mixing salt solution in the deionized water; Take by weighing 14.4g NaOH and 3.18g Na again
2CO
3Be dissolved in and be made into the 300mL mixed ammonium/alkali solutions in the deionized water; Low whipping speed is under 500 rev/mins the condition, above-mentioned two kinds of mixing solutionss to be added drop-wise in the 1L there-necked flask that the 100mL deionized water is housed simultaneously, and rate of addition all is 5mL/min; The pH value is controlled between 9.5～10 all the time during this time, and crystallization 12 hours under 65 ℃ of conditions is prepared the magnesia-alumina hydrotalcite material then;
B: the product deionized water thorough washing of steps A preparation, the pH that makes supernatant liquor is 7～8, adds that to be made into solid content after deionized water fully stirs be 2% slurries again;
C: add the PVA that accounts for slurries gross weight 1% in the houghite slurries of step B, fully stirring makes system be even colloidal state shape;
D: the colloidal state slurries of step C are squeezed on the atomizing wheel disc with 1.2 ten thousand rev/mins of high speed rotating with the flow velocity of 6～10mL/min with constant flow pump, and to set spraying drying ingress temperature be 150 ℃, carry out mist projection granulating.
Embodiment 13
A: take by weighing 61.54g Mg (NO
3)
26H
2O, 31.51g Al (NO
3)
39H
2O and 12.78g In (NO
3)
33H
2O is dissolved in and is made into the 300mL mixing salt solution in the deionized water; Take by weighing 23.04g NaOH and 25.44g Na again
2CO
3Be dissolved in and be made into the 300mL mixed ammonium/alkali solutions in the deionized water; Nucleation, crystallization condition are prepared magnalium indium ternary houghite with embodiment 1;
B: the product deionized water thorough washing of steps A preparation, the pH that makes supernatant liquor is 7～8, adds that to be made into solid content after deionized water fully stirs be 2% slurries again;
Add the PVA that accounts for slurries gross weight 1% in the houghite slurries of C: step B, fully stirring makes system be even colloidal state shape;
D: the colloidal state slurries of step C are squeezed on the atomizing wheel disc with 1.2 ten thousand rev/mins of high speed rotating with the flow velocity of 6～10mL/min with constant flow pump, and to set spraying drying ingress temperature be 150 ℃, carry out mist projection granulating.
Claims (3)
1. layered di-hydroxyl composite metal oxidate microspheres, chemical general formula is:
[M
II 1-xM
III x(OH)
2]
x+·(A
n-)
x/n·mH
2O
Wherein, M
IIBe Mg
2+, Ni
2+, Zn
2+, Cu
2+, Co
2+, Ca
2+Or Fe
2+In one or both; M
IIIBe Al
3+, Cr
3+, Ga
3+, In
3+, Co
3+, Fe
3+Or V
3+In any one or two kinds;
The particle diameter of this microballoon between 5～100 μ m, median size d
(0.5)=20～25 μ m, bulk density are 0.4～0.8g/cm
3, specific surface area is at 20～150m
2Between/the g; Pore volume is in 0.1～0.8cm
3Between/the g, the most probable pore size distribution is between 2～40nm; This microballoon is a solid sphere.
2. the preparation method of a layered di-hydroxyl composite metal oxidate microspheres as claimed in claim 1, adopt coprecipitation method, nucleation/crystallization isolation method or non-equilibrium crystallization method or hydrothermal synthesis method earlier, preparation nano level or submicron order layered di-hydroxyl composite metal oxidate (be commonly called as: houghite), it is characterized in that:
The houghite colloidal substances do deionized water thorough washing that A. will prepare but handle without super-dry, the pH that makes supernatant liquor is 7～8, adds that to be made into solid content after deionized water fully stirs be 1～20% slurries again;
The chemical general formula of class neatly is: [M
II 1-xM
III x(OH)
2]
X+(A
N-)
X/nMH
2O
Wherein, M
IIBe Mg
2+, Ni
2+, Zn
2+, Cu
2+, Co
2+, Ca
2+Or Fe
2+In one or both; M
IIIBe Al
3+, Cr
3+, Ga
3+, In
3+, Co
3+, Fe
3+Or V
3+In any one or two kinds;
B: add the tackiness agent that accounts for slurries gross weight 0.5～10% in the houghite slurries of steps A, fully stirring makes system be even colloidal state shape;
Used tackiness agent is a kind of in starch, protein, dextrin, gelatin, synthetic resins, polyvinyl alcohol, the water glass;
C: the colloidal state slurries of step B are squeezed into the flow velocity of 1～30mL/min on the atomizing wheel disc of rotary spray-dryer with constant flow pump, regulated the atomizing wheel rotating speed at 1.0～2.0 ten thousand rev/mins, spraying drying ingress temperature is between 110 ℃～180 ℃.
3. the preparation method of layered di-hydroxyl composite metal oxidate microspheres according to claim 1, it is characterized in that, the spraying drying condition of step Cd is: the atomizing wheel rotating speed is 1.2～1.5 ten thousand rev/mins, and input speed is 5～20mL/min, and inlet temperature is between 140 ℃～160 ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100626496A CN101049953A (en) | 2007-01-12 | 2007-01-12 | Microballons of laminar dual hydroxy composite metal oxide and preparation method |
| PCT/CN2007/070166 WO2008083563A1 (en) | 2007-01-12 | 2007-06-22 | A microsphere of layered double hydroxide and method for preparing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007100626496A CN101049953A (en) | 2007-01-12 | 2007-01-12 | Microballons of laminar dual hydroxy composite metal oxide and preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101049953A true CN101049953A (en) | 2007-10-10 |
Family
ID=38781591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007100626496A Pending CN101049953A (en) | 2007-01-12 | 2007-01-12 | Microballons of laminar dual hydroxy composite metal oxide and preparation method |
Country Status (2)
| Country | Link |
|---|---|
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| WO (1) | WO2008083563A1 (en) |
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| US5364828A (en) * | 1992-10-21 | 1994-11-15 | Minerals Technologies | Spheroidal aggregate of platy synthetic hydrotalcite |
| CN1288078A (en) * | 1999-09-14 | 2001-03-21 | 北京化工大学 | Method for synthesis of well-dispersed and super fine anion laminated material |
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